Patent GB-616694-A (GB)
Title: Manufacture of new amide derivatives
IPC: D06M13/402
Filed: 1944-04-25
Abstract: Amide derivatives are prepared by reacting a mixture of formaldehyde and an aliphatic, cycloaliphatic or aromatic carboxylic acid amide containing at least two directly connected carbon atoms and having at least one amido-hydrogen atom, or the corresponding methylolamide or a functional derivative thereof, with a salt of a basic compound containing the grouping <FORM:0616694/IV(b)/1> and having at least one hydrogen atom attached to a nitrogen atom, if desired, in the presence of an acid.  Specified basic compounds are guanidine, aminoguanidine, dicyandiamidine, biguanide, and basic substitution products thereof such as alkylation or hydroxy-alkylation products or derivatives thereof containing polyglycol ether residues, used in the form of, for example, the acetates, formates, carbonates, nitrates and hydrochlorides. Advantageously, the methylol compound is first formed, for example, by treating a solution of the amide in a solvent such as water, alcohol, acetone, glacial acetic acid, benzene, pyridine or mixtures thereof, with formaldehyde, if desired, in the presence of a condensing agent such as potassium carbonate, trimethylamine or hydrogen chloride, and then reacting the methylol compound with a salt of the basic compound.  Alternatively, the amide, formaldehyde and salt of the basic compound may be reacted together, preferably, with heat and in the presence of a solvent such as dioxane or acetone or a concentrated water-soluble carboxylic acid such as acetic or formic acid, and if desired, with the addition of an acid such as acetic, formic or hydrochloric acid.  A functional derivative of the amide such as the chloromethylamide obtained by reaction of formaldehyde and gaseous hydrogen chloride or of the a  : a 1-dichlorodimethyl ether of the amide, may be reacted with the basic compound salt in like manner.  More than one residue containing an amide group may be introduced into the basic compound when the latter contains more than one hydrogen atom attached to nitrogen. The products, stated to be novel, find use as textile assistants; those containing an aliphatic or cycloaliphatic residue of at least 12 carbon atoms may be used as wetting, softening, foaming or levelling agents, as agents for preventing agglomeration of cellulose fibres or for rendering fibres water-repellent (see Group VIII) and dyeings fast to water. In a typical example (1), stearic acid methylolamide is reacted with guanidine nitrate in glacial acetic acid yielding, after removal of acetic acid, a solid mass which gives a foaming solution with water and is a softening agent for artificial silk; (2)-(5), in like manner, products having similar properties are prepared in excess acetic acid from dicyandiamidine or phenyl-biguanide and oleic acid methylolamide and from a mixture of biguanide and guanidine nitrates, obtained by heating together dicyandiamide and ammonium nitrate, and stearic or oleic acid methylolamide.  Viscose silk is softened by treatment with an aqueous solution of the product of (1) above.  Additional examples of amido starting materials include amides of acetic, acrylic, caprylic, lauric, stearic, linoleic, benzoic, p-stearylaminobenzoic, chloracetic, glycollic, resin and naphthenic acids and N-substituted products of such amides, for example, N-methyl-, N-oxyethyl- and N-dioxypropyl lauric acid amide, as well as urethanes such as octadecylurethane and methylene di-octadecyl urethane.  Specification 616,247 is referred to.  Samples have been furnished under Sect. 2 (5) of the Acts of products prepared as above from octadecylurethane or stearoylaminobenzamide, guanidine nitrate and paraformaldehyde. The Specification as open to inspection under Sect. 91 includes the use of any carboxylic acid amide, uretane, urea, hydrazide or sulphonamide, having at least two directly connected carbon atoms and at least one amido-hydrogen atom, typical additional examples being hexahydrobenzamide, phthalimide, diketopiperazine and ethyl-, phenyl-, dodecyl- and N : N1-didodecylureas.  This subject-matter does not appear in the Specification as accepted.ALSO:Amide derivatives obtainable by reacting a mixture of formaldehyde and an aliphatic, cycloaliphatic or aromatic carboxylic acid amide containing at least two directly connected carbon atoms and having at least one amidohydrogen atom, or the corresponding methylolamide or a functional derivative thereof, with a salt of a basic compound containing the grouping <FORM:0616694/IV (c)/1> and having at least one hydrogen atom attached to a nitrogen atom, if desired, in the presence of an acid (see Group IV (b)) have surface-active properties.  Specified basic compounds are guanidine, aminoguanidine, dicyandiamidine, biguanide and basic substitution products thereof such as alkylation or hydroxyalkylation products or derivatives thereof containing polyglycol ether residues, used in the form of, for example, the acetates, formates, carbonates, nitrates and hydrochlorides. More than one residue containing an amide group may be introduced into the basic compound when the latter contains more than one hydrogen atom attached to nitrogen.  The products, stated to be novel, find use as textile assistants; those containing an aliphatic or cycloaliphatic residue of at least 12 carbon atoms may be used as wetting, softening, foaming or levelling agents, as agents for preventing agglomeration of cellulose fibres or for rendering fibres water-repellent (see Group VIII) and dyeings fast to water. In a typical example (1), stearic acid methylolamide is reacted with guanidine nitrate in glacial acetic acid yielding, after removal of acetic acid, a solid mass which gives a foaming solution with water and is a softening agent for artificial silk; (2)-(5), in like manner, products having similar properties are prepared in excess acetic acid from dicyandiamidine or p  phenyl-biguanide and oleic acid methylolamide and from a mixture of biguanide and guanidine nitrates obtained by heating together dicyandiamide and ammonium nitrate, and stearic or oleic acid methylolamide.  Viscose silk is softened by treatment with an aqueous solution of the product of (1) above.  Additional examples of amido starting materials include amides of acetic, acrylic, caprylic, lauric, stearic, linoleic, benzoic, p-stearylaminobenzoic, chloracetic, glycollic, resin and naphthenic acids and N-substituted products of such amides, for example, N-methyl-, N-oxyethyl- and N-dioxypropyl lauric acid amide, as well as urethanes such as octadecylurethane and methylene di-octadecyl urethane.  Specification 616,247 is referred to.  The Specification as open to inspection under Sect. 91 describes amide derivatives obtainable as above, but derived from any carboxylic acid amide, urethane, urea, hydrazide or sulphonamide, having at least two directly connected carbon atoms and at least one amido-hydrogen atom, typical additional examples being hexahydrobenzamide, phthalimide, diketopiperazine and ethyl-, phenyl-, dodecyl- and N : N1-di-dodecyl-ureas.  This subject-matter does not appear in the Specification as accepted.